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Proven On-Site Analysis of Gaseous Fuels With Analytical Laboratory Precision Increases

Productivity and Allows You to Meet Important Schedule Milestones
Mr. Mitchell Martin, Texas OilTech Laboratories, Inc. and
Mr. Jeffrey C. Mocsari, Siemens Westinghouse Power Corporation
High quality on-site analysis of gaseous fuels is now available. Technological advances in the
field of gas analysis have created the opportunity to perform precision tests never before possible
outside of a controlled laboratory setting. Portable, high speed, ultra-sensitive, micro-gas
chromatographs (micro-GC’s) allow for the simultaneous analysis of complex gas streams, such
as the natural gas used in gas turbines at the power plant construction site. On-site testing of fuel
will change the way you operate and can save your company time and money.
Fuel gas is almost universally analyzed in accordance with the procedures developed by the
American Society for Testing Materials, specifically Method ASTM D 1945-03, “Standard Test
Method for Analysis of Natural Gas by Gas Chromatography”. This complex set of instructions
for the analysis of natural gas also details and establishes precision standards for data
repeatability and reproducibility. Most gas turbine manufacturers mandate this test method and
it meets the American Society of Mechanical Engineers, ASME Performance Test Code
requirements for gaseous fuel analysis. Appendix A of this report provides a very basic
overview of the formulae involved in ASME PTC 22-1997: “Performance Test Code on Gas
Turbines” and ASME PTC 46-1996: “Performance Code on Overall Plant Performance”. Both
of these codes establish the three basic performance measurements required for the calculation of
thermal efficiency of the engine and the overall plant cycle, i.e., 1) the power output, 2) the rate
of fuel consumption (volumetric or mass basis) (Figure 1) and 3) the heating value of the fuel.
Perhaps the most critical information in determining the efficiency of an engine is the heating
value of the fuel gas. The calculation of fuel heating value (Btu/ft3 or Btu/lbm) requires
knowledge of its molecular composition. In order to achieve this, gas samples are taken in small
high-pressure gas cylinders from the fuel supply-line (Figure 2), or other relevant location, and
shipped to an off-site laboratory for analysis.

Figure 1: This is a typical fuel orifice for measuring the flow of gaseous fuels to a combustion turbine (CT).

This is a schematic of a typical bench gas chromatograph. The GC is a combination of precision temperature-controlled. which are used in conjunction with the multiple columns and switching valves to acquire the data. . stainless steel or special alloys. high-quality gas analyses required sophisticated equipment available only in specially equipped laboratories. It is common to have four or more columns in a typical GC setup.Figure 2: This is a typical fuel sampling port. The columns are made from coated fused silica. detection and measurement of the individual gas components. the TCD and the FID. thin tubes. non-portable device called the gas chromatograph (GC). The typical instrument setup consists of a large. Two detectors are shown. they are coiled Figure 3. Since the columns are long. the cylinder requires pressurization and venting at least three times before taking the final sample. called columns. Historically. with separation. insulated ovens (Figure 3). To ensure quality. Each oven contains one or more long. The instrument performs a function similar to a distillation. varying from 6 to 30 meters in length. It consists of several ovens (in this case four are depicted) with columns.

Numerous comparative evaluations have demonstrated the reliability. From this information. The analytical process concludes with the submission of a final laboratory report to the appropriate plant engineer. However. Table 1 presents a comparison of typical onsite test results to those from subsequent analyses performed at the main laboratory. generally used for the non-combustible gases. . columns. A typical gas fuel analysis on a micro-GC takes 1. When properly calibrated using high quality certified reference gases.5 to 2. A small portion of the plant-site collected gas sample is bled from the cylinder into a specially designed. there are two types of detectors used in gas analysis. depending on the instrument and conditions. which is very sensitive for combustible gases. i. the micro-GC results are analytically equivalent to the results obtained in the laboratory. carbon dioxide and argon. solid-state GC’s. rotating sample port. butane. Compressibility Factor. methane. the calculated heating values. The first is a thermal conductivity detector (TCD). the logistics of shipping cause delays adding several days to the process. ethane. It is possible to run three or more runs in 10 minutes. The instrument also contains chemical detectors. The relative percent differences between the on-site and main laboratory. The micro-GC is capable of performing the same analyses as the large laboratory instruments. The micro-GC can analyze the fixed gases: oxygen. At a given instant. Under good circumstances. and Relative Density of Gaseous Fuels”. Each of the columns contains specially designed materials and coatings called the stationary phase. and is no longer limited to the traditional controlled laboratory. pentane and hydrocarbons greater than hexane (C6+) and their various isomers. “Standard Practice for Calculating Heat Value. hydrocarbons. The ovens. Often. The process continues with the determination of the normalized mole percent of each gas component. fast. carbon monoxide. Normally. there are no significant or practical differences in these results.05% or less than 1 part in 2000. an on-site analysis is performed two or three times to ensure repeatability. The calculated Gross Btu’s per cubic foot were within one Btu. this process usually takes one to two days. high quality gas analysis no longer requires shipping. Compare this analytical time to that of the high-quality. nitrogen. were typically less than 0. propane. the heating value and the specific gravity of the gaseous fuel. same instrument” repeatability specifications set forth in Method ASTM D 1945 and shown in Table 2. It can also analyze the fuel gases: hydrogen. laboratory instrumentation. the valve is rotated and a fixed volume of gas is allowed to enter the instrument. The proper distribution of the sample through the instrument requires the GC to be equipped with several computer controlled switching and back-flushing valves. normally called a universal detector. When used to determine engine efficiency. just as is done at the main laboratory.inside the ovens. on-site analysis of complex gas samples possible through the creation of micro-sized. portable. the on-site micro-GC instrument met the “same operator. In most cases. compressibility factors and specific gravity of the fuel are computed in accordance with Method ASTM D 3588. as displayed in Table 3. which can take approximately 30 minutes for a single test. This provides a suitable surface for the separation of the various components of the complex natural gas mixture. Typically.e.. repeatability and reproducibility of the micro-GC and on-site testing techniques. Recent improvements in technology and equipment miniaturization have made high-quality. The second is a flame ionization detector (FID).5 minutes. valves and detectors all work to separate and acquire the data which can then be quantified and processed with a computer and proprietary software.

443 0.28 1018.451 0.564 1.024 0.458 1.706 2.043 100.788 2.485 0.415 0.532 0.653 0.009 0.023 0.008 0.061 0.443 94.Comparison of On-Site Results with Results from Main Laboratory A B C D 1st Day 2nd Day 14th Day 18th Day Mole % Mole % Mole % Mole % Hydrogen Oxygen Nitrogen Methane Carbon Dioxide Ethane Propane Iso-butane n-Butane Iso-pentane n-Pentane Hexane plus TOTAL% 0.000 0.954 2.059 0.435 94.595 1.061 0.471 94.76 1014.010 0.055 0.637 1.000 Calculated Btu/ft 3 1015.006 0.007 0.055 0.019 100.648 1.031 100.000 0.001 0.062 0.019 0.019 100.020 0.553 1.496 0.29 1018.617 1.445 94.390 0.052 0.005 0.065 0.701 2.430 0.776 2.019 0.000 0.979 2.000 0.408 0.006 0.000 0.021 100.000 0.020 0.443 0.436 0.573 0.415 0.612 0.730 2.006 0.398 94.006 0.000 0.Table 1 .058 0.052 0.768 2.31 1014.598 94.000 0.050 0.000 0.055 0.018 0.000 0.022 0.009 0.058 0.058 0.74 1018.005 0.014 100.005 0.058 0.009 0.001 0.034 100.000 Calculated Btu/ft 3 1016.97 ON-SITE RESULTS PARAMETER FIXED LABORATORY RESULTS PARAMETER .007 0.035 100.80 A B C D 1st Day 2nd Day 14th Day 18th Day Mole % Mole % Mole % Mole % Hydrogen Oxygen Nitrogen Methane Carbon Dioxide Ethane Propane Iso-butane n-Butane Iso-pentane n-Pentane Hexane plus TOTAL% 0.53 1018.682 1.482 94.002 0.007 0.005 0.003 0.410 0.563 94.060 0.

10 The difference between two results obtained by different operators in different laboratories on identical test materials should be considered suspect if they differ by more than the following amounts: Reproducibility.04 0.02 0.0 1.0 5.0 to 10 Over 10 Reproducibility 0.15 .07 0.08 0.1 0. same operator.10 0.12 0.1 0.07 0.01 0.0 to 5.0 1. different instrument: Concentration (mol %) 0 to 0.0 5.1 to 1. same instrument: Concentration (mol %) 0 to 0.0 to 10 Over 10 Repeatability 0.Table 2 – ASTM D 1945: Repeatability and Reproducibility The difference between two successive results obtained by the same operator with the same apparatus under constant operating conditions on identical test materials should be considered suspect if they differ by more than the following amounts: Repeatability.0 to 5. different operator.1 to 1.

29 1018.36 Average Relative % Difference 0.Table 3 . The modules contain a silicon micro-injector.Comparative On-Site versus Fixed Laboratory Reproducibility Sample Acquired On-Site Results Main Laboratory Results Btu/ft 3 Absolute Net Difference Btu/ft 3 Relative Percent Difference Btu/ft 3 A 1st Day 1015.035 This accuracy is possible because there are four individual GC modules in one micro-GC package (Figure 4). an Alumina column (Al) and an OV-1 column to differentiate the lighter and heavier hydrocarbons.74 0.044 D 18th Day 1018.017 Average Absolute Net Difference.054 B 2nd Day 1014.45 0.80 1018.55 0.28 1014. Btu/ft 3 0.53 0. to ensure long-life and column performance. Selected stationary phases in each of the individual columns provide the necessary flexibility to analyze a wide variety of refinery and natural gas samples. The individual systems also contain precolumns with back-flush valves that are capable of venting to the atmosphere. a PoraPLOT U column (PPU).24 0.024 C 14th Day 1018.31 0. The columns typically are a molecular sieve column (MS5A) for the atmospheric gases and methane. a temperature controlled capillary column and a micro-TCD.18 0.97 0. .76 1016. The back-flush valves also function to reduce the analytical cycle time on several of the columns. to keep the analytical times short.

This is a schematic of a micro-gas chromatograph.565 . The micro-GC’s analytical precision is improved compared to conventional systems by virtue of its solid-state construction and by using the same style of injector and detector for each of the GC modules. Table 4 details the quantitative precision and repeatability of the micro-GC over 50 replicates of a prepared gas sample.Figure 4.Quantitative Precision Over 50 Analyses of Gas* Component Column Mol% Deviation Methane Carbon Monoxide Ethane n-Propane iso-Butane iso-Pentane n-Hexane MS5A MS5A PPU Alumina OV-1 Alumina OV-1 4.048 0. Each module contains silicon injectors.363 0.505 0. It consists of four individual modules.100 0. The instrument results are impressive and typically vary by less than 0. Table 4 .005 2. The micro-TCD detector system exhibits high analytical repeatability and low standard deviations.5% relative standard deviation (RSD).0003 *Excerpted from Agilent Technologies.034 0. 5988-6700EN. This allows for consistently repeatable results.246 0.0007 0.238 0.423 0. 2002 %Relative Standard Deviation 0.0020 0.300 0. June 7. Inc. Analytically. valves and micro –thermal conductivity detectors.0004 0.0007 0.0200 0. This gives the micro-GC excellent quantitative precision. The micro-GC also has a phenomenally linear detector response over five orders of magnitude.305 0. This allows the micro-GC to have an extremely accurate linear dynamic range response from 10 ppm to 100 percent for most analytes. columns. this means the micro-GC is capable of providing excellent quality. accurate and timely analyses at the plant site.0150 0. pre-columns.980 0.997 4.

For example. incorrect valve settings. pulses per time. The official test can then be run with a high degree of confidence and minimal potential for re-tests. Real-time heat rate calculations obtained from on-site analytical data can prevent parties from entering into an official test with an error in instrumentation or engine settings that can invalidate the performance test and force a costly re-test. particularly for sites with multiple fuel sources. During a performance test or commissioning trial the on-site micro-GC allows real-time measurement of the fuel composition. line temperature. differential pressure. incorrect thermocouples.) in real time. data from an earlier fuel analysis may be used for calculating an estimated performance. etc.At the plant site. fuel cost. Clearly. timely and accurate fuel analysis allows key commercial and engineering decisions to be made before initiating a critical plant start-up test. In order to determine the fuel composition. This allows for the immediate calculation of efficiency. If available. the plant or the gas supplier may have an inline gas chromatograph. periodic gas samples were taken from the fuel supply line and they were shipped to an off-site laboratory for analysis. incorrect emissions. during engine tuning. problems were discovered that invalidated the test. Historically. this can result in a delta greater than 1% between a preliminary fuel analysis and the actual fuel composition. necessitating the scheduling of a retest. the test instrumentation and engine operation can be scrutinized for errors. If an engine or plant is meeting contractual requirements. the value of on-site fuel analysis can far outweigh the increased initial cost over the historically typical process of off-site lab analysis. Adjustments can be made to the engine or plant to improve the performance shortfalls before initiating an official test. synchronized with the real-time power and fuel flow measurements. and the final calculation of plant efficiency. Due caution must be exercised when making commercial and engineering decisions based on old fuel data. Those values could be reviewed at any time during the test run. the inline-GC data may be useful for preliminary calculations. but referee analyses of fuel samples are still required. engine operating hours and plant personnel. In many cases. worker support. this approach is no longer acceptable. if the engine or plant is not meeting contractual requirements based on the realtime fuel composition. The overall cost for a performance test. Today. and even hidden computer/spreadsheet calculation errors. since fuel supplies can vary over short periods. Many times. Additionally. It is apparent that the fuel composition used for performance test calculations is critical to the accuracy of the final test result. which may or may not be certified or calibrated at the time of a test. However. on-site testing has permitted personnel to uncover problems with contract fuel composition. then the parties can agree to run an official test. or re-test. In addition to the actual cost of the test. In some cases. preliminary testing and before an actual test period. can exceed $40. This created a delay in obtaining the actual fuel composition. the fuel composition can be monitored to detect variations that could adversely affect the out come of the test. Equally. contract performance tests determine the transaction of millions of dollars between the equipment supplier and the customer in the form of final acceptance payments and liquidated damages for performance shortfalls. the normal practice for a typical performance test has been to monitor the power output and raw fuel flow measurements (line pressure.000 for instrumentation. .

Additionally. performance tests and commissioning trials. Typical benefits include: • • • • • • • • • • determination of real time fuel composition flexible and increased sampling frequency greater confidence in test results discovery of hidden critical problems timely data reporting test results to the buyers on the same day final sign-off with the buyer minimized necessity for retesting reduced personnel time at the plant site flexible reporting format On-site testing has proven to be a logical approach for providing time-critical and cost-critical analytical results to the engineers responsible for startups. and the use of domestic laboratories is questionable or unreliable. The advantages of on-site micro-GC gas analysis are its: speed. on-site fuel analysis is also recommended. accuracy. in today’s political climate. Many international sites experience difficulties and significant delays when shipping hazardous materials such as compressed gas fuel samples back to the United States. In some cases where transport to a lab in the USA is not possible. Companies that have used on-site testing and the engineers responsible for the outcomes of those tests have been very pleased with the benefits they obtained. . and in some cases necessitated by the inability to transport gas cylinders. on-site fuel analysis is the only viable method for obtaining valid fuel composition analysis. precision and reliability.

typically in lbm/hr HVp = heating value of fuel at constant pressure. typically in Btu/lbm. the heat input is determined by &(HV p ) + SH p Heat Input = m where m& = fuel mass flow rate. SHp = sensible heat at constant pressure in Btu/hr referenced to 60°F and 14. In North America. CC thermal performance tests are run per ASME PTC-46-1996 (2). GT thermal performance tests are typically run in accordance with the ASME Test Code PTC-22-1997 (1). the composition is required to calculate the heating value of the gas per ASTM D 3588. Heating value must be identified as high heat value (HHV) or low heat value (LHV). which are required to calculate gas density. In both codes thermal efficiency is defined as: η= Power Output Heat Input In North America. The gas composition is required to determine the molecular weight of the gas and the compressibility factor. (2) • For constant pressure heating value. In all cases gas density at the meter is required to determine mass flow rate. Heat rate is the reciprocal of efficiency HR = Heat Input Power Output For tests run on gaseous fuel.696 psia. The composition of the fuel gas at the time of the test is required to determine the three parameters used to calculate the Heat Input: • Fuel mass flow rate is measured by a flow meter. typically an orifice meter or a turbine flow meter. . Heat Rate (HR) is the working standard for depicting engine and plant efficiency.APPENDIX A On Site Fuel Gas Analysis: Plant Performance Testing The composition of fuel consumed during the thermal performance test for a gas turbine engine (GT) and for a combined cycle plant (CC) is one of the three basic performance measurements required to determine the thermal efficiency of the engine and overall plant cycle. (1).

American Society for Testing Materials. and Relative Density of Gaseous Fuels”. (2) ASME PTC 46-1996: “Performance Test Code on Overall Plant Performance”. Fuel composition can be monitored during the test to detect any variations in fuel composition and since the micro GC technology meets the ASME Performance Test Code requirements for gaseous fuel analysis. the remainder of gas in the cylinders can then be saved for confirmation of the on-site fuel analyses. American Society for Testing Materials. which directly corresponds to the real time power and fuel flow measurements. Compressibility Factor. 1997. Samples may be taken and analyzed every 15 minutes. . The fuel sampling and analysis process with an onsite analyzer is very similar to the process used for off-site lab analysis. (3) ASTM D 1945-03: “Standard Test Method for Analysis of Natural Gas by Gas Chromatography”. American Society of Mechanical Engineers. American Society of Mechanical Engineers. 1997. References: (1) ASME PTC 22-1997: “Performance Test Code on Gas Turbines”. (4) ASTM D 3588-98: “Standard Practice for Calculating Heat Value. The micro-GC technology at a site allows real time measurement of the fuel composition.• For sensible heat. final performance results can be generated at site shortly after the completion of the test. Since the microGC uses a small fraction of the gas sample. Fuel samples are taken from the gas supply line in high-pressure sample cylinders typically used for off site lab analysis. This allows for real time analysis of the heat rate with a high degree of confidence and minimal risk of results shifting due to incorrect preliminary fuel composition. the composition is required to determine the enthalpy of the fuel gas mixture. The sample cylinders are processed on site by the micro-GC and analysis reports are printed upon completion of the analysis.